Determination of Carbon and Nitrogen Isotope Fractions in Asparagine, Aspartic Acid, Threonine and Methionine

The nomenclature for compounds that are modified with isotopes is growing every day. Compounds can be modified with isotopes either individually, in a functional group or groups, or completely with all atomic centers of the element. This diversity of isotope-modified compounds increases the range of researches that can be studied using them. Compounds modified with isotopes of carbon-13 or nitrogen-15 can be converted into carbon monoxide, carbon dioxide and molecular nitrogen. Currently, only the average value of carbon-13 or nitrogen-15 isotopes can be determined. However, by directly determining the atomic share of these isotopes in organic compounds modified with isotopes, information about the isotopic centers of the element can be obtained. The atomic fraction of an element is defined as a single carbon or nitrogen isotope-modified center or centers, or all centers that are isotope-modified with that element at the same time. Carbon-13 or nitrogen-15 isotopes’ atomic fraction can be determined molecularly or with fragment ions of different elemental content, or both. This makes the method self-verifying, increasing the accuracy and reliability of the results obtained. Amino acids, such as asparagine, aspartic acid, methionine, and threonine, are essential for the human body. This proposed method of isotopic analysis will increase the possibilities for scientific research using these compounds.

Microwave-assisted Synthesis of Modified Polyaspartic Acid in Solvent

Polyaspartic acid(PASP)is suitable for the inhibition of scale deposition from water.To enhance its in- hibition efficiency,PASP was modified by reacting aspartic acid(Asp)with glutamic acid(Glu)to provide Asp-Glu copolymer under microwave irradiation.The influence of reaction parameters on conversion,molecular weight and inhibition of CaCO3 precipitation was investigated Infra-red.(IR), 1H nuclear magnetic resonance( 1H NMR)and 13C nuclear magnetic resonance( 13C NMR)spectroscopies were used to characterize the copolymer.The results show that copolymerization of aspartic acid and glutamic acid is catalyzed by a small amount of phosphorous acid (H3PO4)in solvent,the product conversion is 98.05%under the following conditions:the molar ratio of glutamic acid to reactant[Glu/(Asp+Glu)]is 0.3 and that of catalyst(Cat)to reactant[Cat/(Glu+Asp)]is 0.05(0.65ml H3PO4),the volume of solvent dimethylformamide is 16ml,the microwave power used is 720W and the reaction for 3 min.The weight average molecular weight of copolymer synthesized under these conditions is 2709 and the inhi- bition rate for CaCO3 is 97.75%.

Poly(ethylenimine)-grafted-poly[(aspartic acid)-co-lysine]: A Non-viral Polymer with Potential for DNA Delivery

A biodegradable gene transfer vector, poly(ethylenimine)-grafted-poly[(aspartic acid)-co-lysine] has been developed by thermal polycondensation of aspartic acid and lysine, and branch poly(ethylenimine) (Mw less than 600) was grafted to the backbone. The polymer was characterized by 1H NMR. It appeared lower cytotoxity compared to poly(ethylenimine) (25KDa), which was quantified by MTT assay. Electrophoresis indicated that the polymer could retardate DNA at N/P ratio 1.2-1.8 (w/w). Transfection efficiency of the complexes was studied in NT2 cell lines. It was 1.5 fold higher than molecular weight PEI (Mw = 25KDa).

Detection of Serine Octamer by Desorption Electrospray Ionization Mass Spectrometry in Resultant Mixture of Aspartic Acid Exposed to Sunshine Under Natural Conditions

Serine, one of the nonessential amino acids, is of principal interest because of its capability to form magic-number ionic clusters, which provide a remarkable preference for homochirality. With L-aspartic acid as the precursor, this study provides experimental evidence for serine formation in weak acidified aqueous solutions in the presence of iron, with exposure to sunlight, which simulates the natural conditions of the prebiotic aqueous environment. The resultant mixture is directly analyzed via desorption electrospray ionization mass spectrometry（ DESI-MS）, without any sample preseparation. The serine monomer is successfully detected as protonated molecules, giving a peak at m/z 106, which is confirmed by the MS/MS fragments. Protonated serine octamer（ m/z 841 ） is also observed with significant abundance in the MS spectra and is confirmed by the MS/MS data, which shows the formation of the serine octamer by a synthesized serine in the resultant mixture. It is also found that the serine octamer yielded equivalent abundance in the DESI mass spectra in a wide pH range（pH = 1-5 ）, and that existence of ferrous salt and sunshine are essential for the conversion of aspartic acid to serine in the acidic water solution.

INTRAMOLECULAR β-CARBOXYLIC ACTIVATING OF N-PHOSPHORYL ASPARTIC ACID

The β-carboxylic group plays an important role in the peptide formation,esterification and the ester exchange at the phosphoryl group of N-phosphorylated aspartic acid.

Impact factors and pathways of halonitromethanes formation from aspartic acid during LED-UV_(265)/chlorine disinfection

Light emitting diode (LED-UV)/chlorine disinfection can replace UV/chlorine disinfection in wastewater treatment plants and water supply plants. Halonitromethanes (HNMs) are a class of novel nitrogenous disinfection by-products, which are characterized by higher cytotoxicity and genotoxicity than regulated disinfection by-products. Herein, the impact factors and pathways of HNMs formation from aspartic acid (ASP) were investigated during LED-UV_(265)/chlorine disinfection. The results showed that three types of chlorinated-HNMs (Cl-HNMs) were found during LED-UV265/chlorine disinfection, and their concentrations increased first and then declined as the reaction progressed. Cl-HNMs yields increased with increasing LED-UV_(265) intensity, free chlorine dosage, and ASP concentration, which declined with increasing pH (6.0–8.0). Meantime, the important impact of the coexisting ions contained in water matrices on HNMs formation from ASP was observed during LED-UV_(265)/chlorine disinfection. It was found that copper ions (Cu^(2+)) promoted Cl-HNMs formation. Furthermore, when bromide (Br–) appeared during LED-UV265/chlorine disinfection, nine types of HNMs were detected simultaneously. Moreover, Br– not only converted Cl-HNMs toward brominated (chlorinated)-HNMs and brominated-HNMs but also showed a marked effect on HNMs concentrations and species. Subsequently, the possible pathways of HNMs formation from ASP were proposed during LED-UV_(265)/chlorine disinfection. At last, it was proved that the formation trends of HNMs obtained in the real waters were similar to those in simulated waters. This work elaborated on the influence factors and pathways of HNMs formation, which is conducive to controlling the HNMs produced during LED-UV_(265)/chlorine disinfection.

Mechanism Exploration of Euphorbia fischeriana Steud. for Liver Cancer Based on Aspartic Acid Identification in Metabolomics

Objective:To investigate the anti-liver cancer effects and aspartic acid(Asp)-related action mechanism of Euphorbia fischeriana Steud.(LD).Methods:The mice model of liver cancer was established by injection of H22 cells.After 5 days,mice were randomly divided into model group,sorafenib group(20 mg/kg),LD high-dose(LDH,1.36 g/kg) group,LD medium-dose(LDM,0.68 g/kg) group,and LD low-dose(LDL,0.34 g/kg)group,10 mice each group.Drugs were intragastrically administered to the mice once daily for 10 days,respectively.Body weight,tumor size and tumor weight were recorded.Hepatic index was calculated.Pathological changes of liver cancer tissues were evaluated by hematoxylin and eosin staining and TUNEL staining.Liquid chromatography-mass spectrometer was used to analyze different metabolites between the model and LDH groups.Results:After LD treatment,tumor weight,tumor size and hepatic index were reduced compared with the model group.Necrocytosis and karyorrhexis of tumor cells were found.Moreover,61 differential metabolites(18 up-regulated,43 down-regulated) were affirmed and 20 pathways of KEGG(P<0.05) were gotten.In addition,Bel-7402,HepG2 and H22 cell viabilities were significantly increased after adding Asp into the medium.And then,the cell proliferation effect induced by Asp was ameliorated by LD.Conclusion:The anti-liver cancer efficacy of LD extract was validated in H22 mice model,and inhibition of Asp level might be the underlying mechanism.

Synthesis and characterization of magnetic and luminescent Fe_3O_4/CdTe nanocomposites using aspartic acid as linker

In this study,the preparation of a new kind of magnetic and luminescent Fe3O4/CdTe nanocomposites was demonstrated. Superparamagnetic Fe3O4 nanoparticles were first synthesized by hydrothermal coprecipitation of ferric and ferrous ions,followed by the modification of their surfaces with tetramethylammonium hydroxide（TMAOH） and the chemical activation with aspartic acid.The surface-modified Fe3O4 nanoparticles were then covalently coated with CdTe quantum dots（QDs）,which were modified with mercaptoacetic acid（MPA）,to form the Fe3O4/CdTe magnetic and luminescent nanocomposites through the coordination of the amino groups on the surfaces of Fe3O4 and the carboxyl groups on CdTe QDs.The structure and properties of as-synthesized nanocomposites were characterized.It was indicated that the nanocomposites possessed structure with an average diameter of 40- 50 nm,yellow-green emission feature and room temperature ferro-magnetism.Both the fluorescence and UV-vis absorption spectra of the nanocomposites showed a blue shift comparing with those of CdTe QDs.The mechanism of the blue shift was presented.The nanocomposites retained the ferromagnetic property with a saturation magnetization of 8.9 emu/g.

Generation mechanism of NO_(x)and N_(2)O precursors(NH_(3)and HCN)from aspartic acid pyrolysis:A DFT study

In order to better understand the mechanism of NO_(x)and N_(2)Oprecursors(NH_(3)and HCN)from aspartic acid(Asp)pyrolysis,decomposition reaction networks resulting in the generation of NH_(3)and HCN were investigated by employing density function theory methods.After several pathways were analyzed in detail,two series of pyrolytic reactions containing three possible pathways were proposed.All the reactants,transition states,intermediates and products were optimized,also the electronic properties on these crucial points were discussed,which shows that Cαacts as the most active site to initiate the pyrolysis reaction,where the direct Cα-Cβbond breakage,due to the atomic charge population of repulsion,led to one key route for the generation of HCN,and the transfer of Hαfrom Cαto Cβresulting in another key route for the generation of HCN,while the transfer of Hαfrom Cαto N atom of Asp resulting in the key route for the generation of HN3.Further,the kinetic analysis based on speed control method in each key reaction pathway was conducted to further compare the generation of HCN and NH_(3)under various temperatures.The above results are in accordance with the related experimental results.

SYNTHESIS OF POLY(GLUTAMIC ACID-co-ASPARTIC ACID) VIA COMBINATION OF N-CARBOXYANHYDRIDE RING OPENING POLYMERIZATION WITH DEBENZYLATION

The random copolymers of glutamic acid （LG） and aspartic acid （ASP）, poly（LG-co-ASP）, with designed compositions could be successfully synthesized via combination of N-carboxyanhydride ring opening copolymerization with debenzylation. Ring opening copolymerizations of y：benzyl-L-glutamate N-carboxyanhydride （BLG-NCA） and β-benzyl-Laspartate N-carboxyanhydride （BLA-NCA） were carried out by using different amines including triethylamine （TEA）, diethylamine, n-hexylamine （NHA）, triphenylamine, diphenylamine or aniline as initiators. All the 6 amines were highly efficient to get well-defined poly（BLG-co-BLA） copolymers with designed compositions although the polymerizations proceeded via different mechanisms （normal amine mechanism or/and activated monomer mechanism）, which are based on chemical structure of amines. The molecular weights of poly（BLG-co-BLA） copolymers could be mediated by both TEA concentration and polymerization time. Then, debenzylation ofpoly（BLG-co-BLA） copolymers was conducted to prepare the corresponding hydrophilic random eopolymers of poly（LG-co-ASP） with a-subunit structure in ASP structural units. The contents of LG structural units in poly（LG-co-ASP） copolymers matched with those of BLG-NCA in NCA-monomer feeds in ring opening copolymerizations initiated by NHA or TEA and were closed to the theoretical line. The diblock copolymer of poly（BLG-b-BLA） could also be synthesized via living NCA ring opening copolymerization by sequential addition of BLG- NCA and BLA-NCA.

Development of aspartic acid ligation for peptide cyclization derived from serine/threonine ligation

Based on a mechanism analogous to the serine/threonine ligation, the aspartic acid ligation, which is facilitated by the γ-amino alcohol based ligation and oxidation, is developed and applied to the synthesis of cyclic peptides. The γ-hydroxyl group triggers the ring-chain tautomerization via a 6-endo-trig process,while the δ-hydroxyl group facilitates the oxidative cleavage of the vicinal diol to give carboxylic acid.

Identification of Aspartic Acid Enantiomers Based on Molecularly Imprinted Polyaniline

Affinity sites for L-aspartic acid （L-Asp） in polyaniline （PAn） were created by two successive processes： first, L-Asp was simply added as template molecules during the polymerization of aniline; second, L-Asp incorporated in PAn backbone was extracted by solvent. PAn with cavities complementary to L-Asp template molecules has been utilized for enantioselective recognition of L- and D-Asp. Enantioselectivity of the imprinted PAn could be attributed to the cavities in the imprinted PAn which was complementary to L-Asp templates both in shape and in positioning of groups. Also in this paper, the structural changes before and after extraction of L-Asp templates were revealed by Fourier-transform infrared （FTIR） spectrum.

Preparation and in vitro cytotoxicity study of poly (aspartic acid) stabilized magnetic nanoparticles

Biocompatible magnetic nanoparticles were prepared by co-precipitation method in the presence of poly(aspartic acid)(PAsp)as stabilizer,which was one of the most extensively studied and used poly(amino acids).As a biocompatible dispersant,PAsp was successfully attached to the Fe_(3)O_(4) nanoparticles,which was approved by Fourier transform infrared spectroscopy(FTIR),transmission electron microscopy(TEM)and thermogravimetric analysis(TGA).From X-ray diffraction(XRD)and vibrating sample magnetometry(VSM)measurement results,it was found that PAsp stabilized iron oxide nanoparticles possess excellent Fe_(3)O_(4) crystal structure and superparamagnetic property.Compared with trisodium citrate stabilized magnetic nanoparticles,PAsp stabilized magnetic nanoparticles were biocompatible and with lower cytotoxicity,which makes it more applicable in medicine,biology and biomaterial science.

Preparation and Characterization of Orally Fast-Disintegrating Mini-Tablets Containing Diphenhydramine Hydrochloride and Aspartic or Glutamic Acid as an Umami Amino Acid

The aim of this study was to prepare diphenhydramine hydrochloride (DPH)-loaded orally fast-disintegrating mini-tablets (OFDMTs) containing either L-aspartic acid (Asp) or L-glutamic acid (Glu) as bitterness-suppressant, to characterize the prepared tablets and to evaluate their bitterness under conditions mimicking those of the oral cavity. The preparation of five formulation batches of the OFDMTs involved mixing DPH, with or without two different concentrations of Asp or Glu, and a premix containing a disintegrating agent. When all ingredients were well mixed, the mixture was directly compacted to form small (4 mm diameter) DPH-loaded OFDMTs. There were only small differences between the tablets with respect to mass, diameter, width and hardness. The disintegration times of the five formulation batches of DPH-loaded OFDMTs were measured using the OD-mate, a disintegration test apparatus in which conditions resemble those of the oral cavity. The disintegration times were all within 10 s of exposure to a medium representing the inside of the oral cavity. Rapid release profiles were observed for DPH, Asp and Glu in these dissolution tests. The taste sensor outputs of samples taken at different times (5 - 30 s) from the dissolution test solutions of the four DPH-loaded OFDMTs containing Asp or Glu were significantly inhibited compared with those of control DPH-loaded OFDMT. These results suggest that the inclusion of Asp or Glu in DPH-loaded OFDMTs is sufficient to mask bitterness in the oral cavity for the first 30 s after the tablet is placed in the mouth. It is anticipated that swallowing will have taken place within 30 s.

Effects of the Amino Acids of Aspartate Family on the Biosynthesis of CoQ_(10) in Rhodopseudomonas palustris J001

[Objective]The study aimed to investigate the effects of the amino acids of aspartate family on the biosynthesis of CoQ10 in Rhodpseudomonas palustris J001.[Method]The impacts of amino acids of this family on the biosynthesis of CoQ10 in Rhodopseudomnas palustris J001 were investigated by feeding these amino acids at the end of the logarithmic phase during incubation,which aim was for the optimization of the fermentation medium and genetic improvement of the strain for CoQ10 production.[Result]The results showed that feeding proper amount of methione(125 mg/L)could increase CoQ10 production by 20.2%,but feeding of lysine(above 500 mg/L),threonine(above 400 mg/L)and/or isoleucine(above 400 mg/L)repressed the biosynthesis of CoQ10.The results indicated that the aspartate kinase is subject to feedback inhibition or repression by lysine,threonine and isoleucine in the strain,which was unfavorable to the formation of methioine and then caused the decrease of CoQ10 production.[Conclusion]Lysine,threonine and isoleucine auxotrophic mutants with resistance to analogues of lysine,threonine and isoleucine could increase the production of CoQ10.

Highly efficient synthesis of β-amino esters via Mannich-type reaction under solvent-free conditions using ZnCl_2 catalyst

β-Amino esters were synthesized via ZnCl2-catalyzed Mannich-type reaction of imines and malonate esters under solvent-free conditions in 6 min. The β-amino ester was converted into the corresponding aspartic acid derivatives.

Comparison of corrosion resistance of MgAl-LDH and ZnAl-LDH films intercalated with organic anions ASP on AZ31 Mg alloys

The aspartic acid(ASP),an environment-friendly corrosion inhibitor,was explored to intercalate into the ZnAl-layered double hydroxide(ZnAl-LDH)and MgAl-LDH coatings on AZ31 magnesium alloys by a facile one-step hydrothermal method.The morphology,composition,structure and corrosion resistance of the prepared coatings were comparatively investigated.It is found that the uniform and dense layered nanosheet(NS)vertically grows on the substrate,and the MgAl−ASP-LDH films exhibit a three-dimensional(3D)rose-like sheet structure with high ratio of pore coverage.The MgAl−ASP-LDH coating exhibits better corrosion resistance and durability of longtime immersion than ZnAl−ASP-LDH coating.The corrosion current density of two coatings is two or three orders of magnitude lower than that of bare Mg alloy,indicating that ZnAl/MgAl-LDH films intercalated with organic ASP anions can significantly improve the corrosion resistance of Mg alloy.

Metabolic Changes in Rats with Photochemically Induced Cerebral Infarction and the Effects of Batroxobin:A Study by Magnetic Resonance Imaging,~1H-and ^(31)p-Magnetic Resonance Spectroscopy

Metabolic changes in rats with photochemically induced cerebral infarction and the effects of batroxobin were investigated 1, 3, 5 and 7 days after infarction by means of magnetic resonance imaging (MRI), 1H- and 31P-magnetic resonance spectroscopy (MRS). A region of T2 hyperintensity was observed in left temporal neocortex in infarction group and batroxobin group 1, 3, 5 and 7 days after infarction. The volume of the region gradually decreased from 1 day to 7 days after infarction. The ratio of NAA/Cho + Cr in the region of T2 hyperintensity in the infarction group was significantly lower than that in the corresponding region in the sham-operated group 3, 5 and 7 days after infarction respectively (P

Enhancement of corrosion resistance of AZ31 Mg alloys by one-step in situ synthesis of ZnAl-LDH films intercalated with organic anions(ASP, La)

Inserting corrosion inhibitors into a lamellar protective coating is an effective way to improve the corrosion resistance of metal substrates.In this work,two kinds of environmentally friendly organic acid anions,aspartic acid(ASP)and lauric acid(La),were explored as corrosion inhibitors to in situ intercalate into the Zn Al-layered double hydroxides(Zn Al-LDHs)on AZ31 magnesium alloys by a facile one-step hydrothermal method.The morphology,composition,structure and the corrosion resistance of these two LDHs coating before and after corrosion experiment were investigated.It is found that both the two kinds of Zn Al-LDHs films consist of uniform and dense layered nanosheets(NSs),and the NSs of ZnAl-ASP-LDHs films grow vertically,but those of ZnAl-La-LDHs films exhibit a staggered tilted structure.The corrosion current density of the two Zn Al-LDHs films are two orders of magnitude lower than that of Mg alloy substrate.After one week’s immersion in NaCl solution,the NSs structure of two kind of ZnAl-LDHs films still remains the uniform and densely coverage on Mg alloy.Owing to the larger d(003)spacing,the ZnAl-La-LDHs have better ability to absorb Cl-and release interlayer anions than Zn Al-ASP-LDHs.These results indicate that the Zn Al-LDHs films intercalated with organic anions,specially La anions,can significantly improve the corrosion resistance of Mg alloy.

Piezoelectric transmission spectroelectrochemistry with a normal piezoelectric quartz crystal as an optically-transparent electrode

Piezoelectric transmission spectroelectrochemistry (PTSEC), i.e., the combination of electrochemistry and spectroelectrochemistry (SEC) with electrochemical quartz crystal microbalance (EQCM) technique is reported by using a normal piezoelectric quartz crystal (PQC) as an optically-transparent electrode (OTE). A theoretical relationship between the PQC response and the spectroelectrochemical response is derived and used to estimate the apparent molar absorptivity of the absorbing species deposited on the OTE on the PQC surface. The complex of copper with aspartic acid is used to test this new PQC-SEC technique. Results show that the combination of three such diverse techniques provides a very useful methodology for studying electrode processes and electrode surface characteristics in situ.